Sulfuric Acid → Methyl 3-bromo-4-methoxy-5-nitrobenzenepropanoate

HRID 2378537Notes

Reaction equation

HRID 2378537 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH:5]=[CH:6][C:7]=1[O:8][CH3:9].[N+:16]([O-])([O-:18])=[O:17].[K+].S(=O)(=O)(O)O.[OH-].[Na+]>C(OC(=O)C)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]([CH2:10][CH2:11][C:12]([O:14][CH3:15])=[O:13])[CH:5]=[C:6]([N+:16]([O-:18])=[O:17])[C:7]=1[O:8][CH3:9]

Participants

6

Reactant 4

HCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 24434Potassium NitrateHCID 22559138HCID 22559138, compound

Product 1

HCID 22559076Methyl 3-bromo-4-methoxy-5-nitrobenzenepropanoateYield 73.2%

Reagents, catalysts & solvents 1

HCID 7918Acetic AnhydrideSolvent

Procedure

A solution of Intermediate 20 (3.20 g) in acetic anhydride (25 ml) was added with potassium nitrate (1.30 g) under ice cooling and stirred for 10 minutes, and the solution was added dropwise with concentrated sulfuric acid (730 μl) over 10 minutes. The reaction mixture was stirred for 10 minutes for 10 minutes at the same temperature, then warmed to room temperature, and further stirred for 30 minutes. The reaction mixture was poured into 1 N aqueous sodium hydroxide (250 ml) containing ice, and extracted with isopropyl ether (200 ml×2). The organic layer was successively washed with saturated aqueous sodium hydrogencarbonate, saturated aqueous ammonium chloride, and saturated brine and dried, and then the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (Quad, hexane:ethyl acetate=10:1) to obtain the title compound (Intermediate 21, 2.73 g).

Workup

  1. stirringThe reaction mixture was stirred for 10 minutes for 10 minutes at the same temperature
  2. stirringfurther stirred for 30 minutes
  3. additioncontaining ice
  4. extractionextracted with isopropyl ether (200 ml×2)
  5. washThe organic layer was successively washed with saturated aqueous sodium hydrogencarbonate, saturated aqueous ammonium chloride, and saturated brine
  6. customdried
  7. customthe solvent was evaporated under reduced pressure
  8. customThe residue was purified by column chromatography (Quad, hexane:ethyl acetate=10:1)

Sources & evidence

ORD record
ord-9caa8140ebc0437fbe0640feb512dbbe
Source dataset
uspto-grants-2008_12
Patent number
US07470807B2

Reaction notes

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